Aluminium soaps and their production



United States Patent Ofifice 3,056,819 Patented Oct. 2, 1962 3,056,819 ALUMINIUM SOAPS AND TIER PRODUCTION Hideo Tanabe, Nishinomiya, Japan, assignor to Takeda Pharmaceutical Industries, Ltd., Osaka, Japan N Drawing. Filed Dec. 16, 1958, Ser. No. 780,687 Claims priority, application Japan Dec. 21, 1957 18 Claims. (Cl. 260-414) This invention relates to a method for preparing aluminium soap and to new aluminium compounds of fatty acids.

Aluminium soap is the general name of aluminium compounds of higher fatty acids and its composition may be represented by Al(RCOO) the corresponding fatty acids being of the formula RCOOH. In fact, however, aluminium soap consisting of aluminium and a fatty acid in a ratio of 1:3 is highly unstable and its preparation is very diificult. In the aluminium soap used in industries, the ratio between the two components is 1:2 or 1:1. When aluminium soap is manufactured by the usual methods, the product mainly comprises aluminium and a fatty acid in a ratio of 1:2 or 1:1, but it contains aluminium soap with other compositions in many cases, so it is difiicult to manufacture aluminium soap with a definite composition.

Known aluminium soap is manufactured by any of the following three methods:

(1) Reaction between an aluminium salt and alkali soap in an aqueous solvent.

(2) Reaction between aluminium hydroxide and a fatty acid in an aqueous solvent.

(3) Reaction between an aluminium alkoxide and a fatty acid in a non-aqueous solvent.

In all the methods, the reactants are subjected to double decomposition, but double decomposition in a nonaqueous solvent is not always suitable for industrial manu facture of aluminium soap because it requires complicated procedures. As mentioned above, the aluminium soap prepared by double decomposition in an aqueous solvent does not have the composition of Al(RCOO) but it mainly contains aluminium and a fatty acid in a ratio of 1:2. It was also confirmed that the product contains soap consisting of aluminium and a fatty acid in a ratio of 1:1, and this may be due to the following reason. In an aqueous solution of an aluminium salt there exists aquo-aluminium ion and its ligand water is dissociated by alkali to produce hydroxo-aluminium ions with various basicities. And if a fatty acid is added to the solution, the hydroxo-aluminium ions combine with the acid and therefore the resulting aluminium soap does not have a definite composition.

The present inventor has found that when a basic aluminium salt with a definite basicity is prepared in advance and then the salt is allowed to react with a fatty acid alkali salt or with a fatty acid alkali salt and alkali, the resulting aluminium soap has always a definite composition. That is, the present invention relates to a method for preparing aluminium soap, which comprises reacting a basic aluminium salt with a fatty acid alkali salt or with a fatty acid alkali salt and alkali in an aqueous solvent. As will be described later, various hydroxoaluminium ions having a definite basicity, respectively can be readily prepared. Hence, if they are reacted with a desired amount of a fatty acid alkali salt or a fatty acid alkali salt and alkali, it is possible to manufacture various kinds of pure aluminium soap containing aluminium and a fatty acid in different ratios such as 1:2, 1:1, 1.511, and 2:1. Manufacture of such kinds of aluminium soap as contain aluminium and a fatty acid in ratios of 8:3, 3:1, 4:1, 5:1, etc. is also possible according to the present method. Of these kinds of aluminium soap, those which contain aluminium in ratios over 2:1 are manufactured only by the method of the present invention, so they are new compounds, and consequently a part of the present invention also relates to those kinds of aluminium soap which contain aluminium in ratios over 2:1.

Basic aluminium salts used in the method of the present invention are prepared profitably by the following methods: (1) an amount more than equivalent of metallic aluminium is reacted with an inorganic acid in water, (2) an amount more than equivalent of aluminium hydroxide is reacted with an inorganic acid in water, (3) an amount less than equivalent of alkali is reacted with an aqueous solution of an aluminium salt, (4) an aqueous solution of an aluminium salt is passed through an anion exchange resin. The inorganic acids used in the above methods (1) and (2) are monobasic acids, most profitably hydrochloric acid or nitric acid, and the aluminium salts used in the above methods (3) and (4) are monobasic acid salts most profitably aluminium chloride or aluminium nitrate. The solutions of the basic aluminium salts obtained as above may be used as such as the material in the present invention, but they may be concentrated or the salts isolated in solid form, if necessary. Basic aluminium salts are generally prepared in an aqueous solvent and since the method of the present invention is profitably conducted in an aqueous solvent, it is unnecessary to isolated the resulting basic aluminium salts for conducting the present method.

The composition of the basic aluminium salt prepared by the use of a monobasic inorganic acid or a monobasic inorganic acid salt may be represented by the general formula of Al ,,(OH) X wherein n represents a positive integral number and X represents a monobasic acid radical. The basic aluminium salt representable by the general formula, Al (OH) ,,X is dissociated in aqueous solution into an inorganic acid ion and a basic aluminium ion, which is formed by the ligandolysis of aquoaluminium ion, [Al(OI-l having 6 moles of ligand water. Aquo-aluminium ion has the property to form polynuclear complex ion through the intermediation of the OH or so-called -ol-bridge produced by ligandolysis, and according to the extent of the ligandolysis, the ratio between aluminium and OH in the resulting ion changes infinitely and the charge of the ion also changes simultaneously. The relation between the composition of the resulting ion and its charge may be represented by the general formula, [Al (OH) (OH) The Y-value of the basic aluminium ion depends upon the n-value of Al (OH) X and therefore the charge of the ion also depends upon the n-value. The initial ion produced in this way is represented by the formula [Al(OH)(OH which is produced by the replacement of one mole of the ligand water of aquo-aluminium ion [Al(OH by OH" and in which X is equal to 1. The initially produced ion then gradually condenses into a highly condensed aluminium ion, thereby X becoming larger than 1. In this case, the factors which exert influence on the condensation are the concentration, tempera ture and standing period of the solution and the n-value. However, how far the condensation may proceed, the proportion of the number of aluminium atoms to the charge is invariable. In other words, in an aqueous solution of an aluminium salt having the composition of Al (OH) X the proportion of the charge of the resulting basic aluminium ion to the number of the aluminium atoms therein is always the same regardless of the extent of the condensation.

The solutions of basic aluminium salts prepared by the methods mentioned before, especially those which were prepared at a low temperature, are not in the satisfactory state for the condensation, but they can be used for the manufacture of aluminium soap. In general, however, a solution containing more condensed ions produced by heating the solution or by other means is more suitable because it gives a readily crystallizable product.

As mentioned before, the n-value in the formula, Al (OH) X which shows the composition of a basic aluminium salt, has direct relation with the Y-value in the formula, [AI (OH) (OH which shows the relation between the composition of the resulting basic aluminium ion and its charge, and therefore the n-value governs the charge of the basic aluminium ion. That is, When n in a basic aluminium salt is 1, the salt may be represented by the formula, Al(OH)X from the general formula, Al (OH) X and therefore its basic aluminium ion may be shown by the formula, [Al(OH) (OI-I the charge of which is 2 to one atom of aluminium. Thus, when n in a basic aluminium salt, Al (OH) X is 2, the salt may be represented by the formula Al (OH) X or Al (OH) X and the charge of its basic aluminium ion is to one atom of aluminium. In this way, it is possible that there exist many basic aluminium salts which are able to produce various basic aluminium ions with different charges as shown below, for example.

n 3 5( 9X5 charge 2 n: 4 A1 6(OH)12X6 charge 1 n: 5 17( charge 1' n: 6 A1s( chargeg n=10 A 12( charge n=14 A11@( charge; 11:16 AIM M charge 2 n=22 AI JOIED X charge n=28 A 3o( charge As mentioned before, in the method of the present invention, basic aluminium salts having a definite composition respectively are used as material in the method of the present invention, and they are profitably prepared by the following methods according to the proportion between the aluminium and inorganic acid in the desired basic aluminium salts.

(1) Metallic aluminium is reacted with a monobasic inorganic acid in a desired proportion. For example,

when the proportion between aluminium and the acid is nzm, n-mole of aluminium is reacted with m-mole of the inorganic acid. Likewise, a basic aluminium salt in which the ratio between aluminium and the acid is 1:2 is prepared by reacting one mole of metallic aluminium with two moles of the inorganic acid. The reaction in this method may be shown by the following equation wherein n and m are an optional integral number respectively (but n:m 1:3) and X is a monobasic inorganic acid.

This method is suitable when the value of mm i comparatively small, especially when the value is smaller than 2: 1.

(2) For the preparation of a solution of a basic aluminium salt in which the value of mm is larger than 2: 1, a proper amount of alkali for example sodium hydroxide solution i added to the solution of the basic aluminium salt prepared by the method (1). In this case, when the alkali hydroxide solution is added gradually to the solution withstirring, a precipitation deposits, which, however,

goes again into solution to make a solution of a higher basic aluminium salt.

This is explained in more detail as follows. The preparation of a solution of a high basic aluminium salt in which the ratio between aluminium ion and anion of monobasic inorganic acid is mm by addition of an alkali solution to a solution of a basic aluminium salt in which the above ratio is x: y comprises adding a solution of mole of the alkali to a solution of m/x mole of the basic aluminium salt to be used as material. This reaction is represented by the equation wherein X is a monobasic inorganic acid, M is an alkali metal, and x, y, m, and n are all integral numbers and they are in the relation of x:y m:n. For example, the reaction between a basic aluminium salt and an alkali hydroxide representable by Al (OH) X and MOH respectively may be shown by the general equation and the reaction between Al (OH) X and MOH by the general equation Consequently, a solution of a high basic aluminium salt with optional basicity can be prepared by the reaction of a basic aluminium salt and alkali hydroxide as mentioned above.

(3) Furthermore, when the solution of the basic aluminium salt prepared by the method (1) or (2) is dialyzed using semipermeable membrane, the anion in the solution is dialyzed out, leaving a high basic aluminium salt in the solution. That is, when one mole of a basic aluminium salt representable by the formula, Al (OH) X in which x, y, m, and n are arbitrary positive integral numbers satisfying the relation of x:y m:n, is dialyzed until mole of anion is dialyzed out,

mole of OH anion combines with the remaining basic aluminium ion to form x/m mole of basic aluminium salt having the composition of Al (OH) X For example, when one mole of a basic aluminium salt having the composition of Al (OH) X is dialyzed against flowing water until 6 mole of anion is dialyzed out, there is obtained a solution of a basic aluminium salt having the composition of Al (OH) X. In this way, it is theoretically possible to produce basic aluminium salts with higher basicities. However, as basic aluminium salts become unstable with the increaseof their basicity, it is practically difiicult to produce basic aluminium salts with very high basicities, and the method of the present invention does not require a basic aluminium salt with such a high basicity.

In the method of the present invention, aluminium soap is manufactured by the reaction of a solution containing a basic aluminium ion having a definite basicity with a fatty acid alkali salt or with a fatty acid alkali salt and alkali as mentioned before.

The fatty acid alkali salt is composed of lauric, myristic, palmitic or stearic acid and sodium or potassium, for example. The reaction between the two reactants does not require a specific condition. It is conducted in water or in an aqueous solvent at room temperature or under heating. As the solvent other than water there may be profitably used a lower aliphatic alcohol, ketone, or ester such as methanol, ethanol, acetone or ethyl acetate. The alkali is used in the form of hydroxide, carbonate or bicarbonate.

The present invention involves the following methods:

(I) Reaction between a basic aluminium salt and a fatty acid alkali salt.

(II) Reaction between a basic aluminium salt, a fatty acid alkali salt and alkali.

As is described below in detail, the method (I) is suitable for manufacturing aluminium soap in which the ratio between aluminium and the fatty acid is about 1-5 :1, and the method (II) is proper for manufacturing aluminium soap in which the proportion of aluminium to the fatty acid is larger.

(I) As was already described in detail, there exist many basic aluminium salts with different compositions, but they may be represented by the general formula Al (OH) X And the charge of the basic aluminium ions produced by the dissociation of the basic aluminium salts depends on the n-value. Hence, if a basic aluminium salt is reacted with a fatty acid alkali salt equivalent to the charge of the formers ion, there occurs double decomposition between them to form a kind of aluminium soap with a definite composition. That is, reaction be tween a solution of one mole of a basic aluminium salt representable by A1,,(OH) X and a solution of y-mole of a fatty acid alkali salt representable by MR (wherein M is an alkali metal and R is a fatty acid) produces one mole of aluminium soap representable by Al (OH) R Reaction of a basic aluminium salt having the composition of Al (OI-I) X, of which n corresponds to 10 in the general formula, with a fatty acid alkali salt representable by MR (wherein M is an alkali metal and R is a fatty acid) proceeds as follows:

and the ratio between aluminium and the fatty acid in the resulting aluminium soap (AI (OH) R) is 2:1.

Likewise, if basic aluminium salts with other compositions are allowed to react with a fatty acid alkali salt equivalent to the charges of the formers ions, there are obtained various kinds of aluminium soap with compositions corresponding to those of the basic aluminium salts.

(11) As mentioned before, basic aluminium salts in .which the proportion of aluminium to anion is larger than 5:1 are unstable and therefore their manufacture is practically very difficult. The method described in (I) is therefore limited for the manufacture of aluminium soap in which the proportion of aluminium to the fatty acid is smaller than 5 :1.

For the manufacture of aluminium soap in which the proportion of aluminium is larger, the following method is profitably employed. Of course, aluminium soap in which the proportion of aluminium to the fatty acid is smaller than 5 :1 can be manufactured by the same method. The method comprises reacting a solution of a basic aluminium salt having an arbitrary composition with less than an equivalent of a fatty acid alkali salt and allowing the remaining anion to react with the equiv- .'alent of alkali. This is also explained as follows. For the manufacture of aluminium soap in which the ratio between aluminium and matty acid is mm from a basic aluminium salt in which the proportion of aluminium to anion is a: m (ft the salt is reacted with nx/ m mole of a fatty acid alkali salt and the remaining nx m mole of anion is replaced with 01-1 when it is reacted with ( J2 y m mole of alkali. This reaction may be represented by the equation:

More particularly, the reactions for the manufacture of those kinds of aluminium soap in which the ratios between aluminium and a fatty acid are 4:1, 5:1, 8:1 and 16:1 from a basic aluminium salt with the composition of Al (OH) X are explained by the following equations.

(III) In the above-mentioned methods, the anion was always regarded as a monobasic inorganic acid, but basic aluminium salts containing dibasic inorganic acid, such as sulfate, are usable for the manufacture of various kinds of aluminium soap having optional compositions in the same principle as above. For example, when a sulfate ion is added to a solution of a highly condensed basic aluminium ion, a sparingly soluble basic aluminium sulfate is precipitated, the sulfuric acid ion of which, however, is removed by the addition of alkali. More concretely, a basic aluminium ion is sufliciently condensed in a solvent and a sulfate (mainly a solution of alkali sulfate is employed) is added to the solution and the resulting basic aluminium sulfate is allowed to react with a fatty acid alkali salt and alkali in a solvent to produce aluminium soap. This procedure may be effected in two ways: (1) To a solution of a fatty acid alkali salt is added alkali and the solution is reacted with the basic aluminium sulfate, (2) the basic aluminium sulfate is first reacted with a fatty acid alkali salt and the remaining anion is removed by the addition of alkali.

For example, reactions for manufacturing such kinds of aluminium soap, in which the ratios between aluminium and a fatty acid rest are 4:1 and 8:1, from a basic aluminium sulfate ([Al (OI-I) SO a fatty acid alkali salt (MR, wherein M is an alkali metal and R is a fatty acid rest) and alkali (MOH) are shown as follows.

(In the case of 4:1)

(In the case of 8:1)

In this way, aluminium soap with any desired composition may be manufactured by properly selecting the amounts of the reactants. In this case, however care should be taken not to use an excess amount of alkali because the reacted fatty acid is removed from the product.

Unlike the aluminium soap prepared by the known methods, the products of this invention have a definite composition respectively, and therefore it may be unnecessary to purify them, but if necessary, they are washed with an organic solvent such as acetone to remove impurities such as free fatty acid.

Among the aluminium soaps prepared by the method of the present invention, aluminium monostearate, andalurninium distearate are known compounds, but those which contain stearic acid in smaller proportion are all not found in the literature.

The properties of compounds consisting of aluminium and stearic, capric, palmitic and lauric acids are as follows.

1. INDEX OF REFRACTION (BY IMMERSION METHOD) AND MELTING POINT 1 All decompose at high temperatures.

2. ANGLES OF DI-FFRACTION OF X-RAYS 17 35002): A1(OH)2(C11H35COz) Products of the Value in the Products of the Valuein the present inv. literature present iuv. literature 3. 35 3. 45 (4. 50) 5. 83 5. 78 10. 50 (9. 7) ll. 55 (l0.

Values in the brackets are a little ambiguous.

As shown in the above list the products of the present invention exhibit a clear angle of diffraction of X-rays respectively, showing that they are highly pure. As far as aluminum stearates for example are concerned, their halo at d==4.27 A. fades and they become from crystalline to amorphous with decrease of the content of the stearic acid therein.

3. INFRARED SPECTRUM Aluminium distearate and aluminium monostearate have absorptions at 10.15, 8.95, 6.28 and 2.70-2.95 and these values are in accord with those in the literature. All the aluminium soaps prepared by the method of the present invention show the absorptions of OH and -COO- at 2.70-2.90,u and 6.30 respectively, establishingthat the respective fatty acids are combined completely.

4. SOLUBILITY The products of the present invention are insoluble in water and other usual solvents, but those which contain fatty acids in high content are soluble in solvents of benzene series, such as benzene and xylene, and vegetable oils, such as sesame oil and olive oil. The solubility of aluminium soaps becomes low with the decrease of the fatty acidcontent therein and part of them remains undissolved in swollen form.

Like the known aluminium monoand di-fatty acid compounds, the products of the present invention are em ployed in the manufacture of lubricant grease, paints, viscosity-increasing agents, caking agents, frosting agents, medicines, water-proofing agents, suspending agents and cement, especially in the rubber industry as accelerator of vulcanization and dispersing agents. And also the products are useful as distributing and reinforcing helper of the silica added to rubber.

The following examples serve merely as illustrative of this invention and do not restrict the scope of the inven tion.

Remarks on the Examples (1) Molecular formulae of basic aluminium chlorides described in the following examples show merely the ratio of their components. In reality, basic aluminium chlorides ready to react with a fatty acid alkali salt are dissociated into chlorine ions and condensed basic aluminium ions with various basicities.

(2) A 1 mole/l. solution of a basic aluminium chloride designates a solution of a basic aluminium chloride, in which the content of aluminium is 1 gram-atom in 1 litre.

(3) Solution means an aqueous solution except otherwise noted.

(4) Temperatures are all uncorrected.

(5) N means concentration of normal unit.

EXAMPLE 1 (1) One tenth mole 2.7 g. of metallic aluminium is dissolved in cc. of 2N-HC1 (0.2 mole) under heating to form a solution of a basic aluminium chloride representable by the formula of Al(OH)Cl (2) To a solution of 47.5 g. (0.1 mole) of potassium alum (AlK(SO (-12H O) is added a solution of sodium bicarbonate. After washing with water, the resulting aluminium hydroxide is dissolved in 100 cc. of ZN-HCl (0.2 mole) and the solution is heated for 1 hour at about 100 C. in a water-bath to obtain a solution of a basic aluminium chloride representable by the formula of Al(OH)C1 (3) To a solution of 24.2 g. (0.1 mole) of hydrous aluminimum chloride in 100 cc. of water is added gradually 8.4 g. (0.1 mole) of sodium bicarbonate with stirring, and the mixture is heated at about 100 C. on a water-bath for 1 hour to yield a solution of a basic aluminum chloride representable by the formula of Al(OH) C1 Any of the solutions of the basic aluminium chloride produced by the above three methods is diluted with water to 200 cc. The diluted solution is added to a solution prepared by dissolving 56.90 g. (0.2 mole) of stearic acid and 8 g. (0.2 mole) of sodium hydroxide in 200 cc. of water under heating on a water-bath. After the product has precipitated, it is washed with water to remove chlorine ion and dried at 100 C. The product is extracted with acetone in Soxhlets extractor to remove free stcaric acid, obtaining 57 g. of aluminium distearate whose formula is Al(OH) (C H COO) Aluminium distearate produced from the basic aluminium chloride prepared by the above method (1):

Analytical value: Al, 4.47% C H COO, 91.28% Ratio of Al:C I-I COO: Calcd. 1:2, found 1:1.943 Melting point: ISO-154 C.

Refractive index: 1.4697 (21 C.)

Aluminium distearate produced from the basic alumi niurn chloride prepared by the above method (2):

Analytical value: Al, 4.54%; C H COO, 91.28% Ratio of AI:'C H COO: Calcd. 1:2, found 111.9133 Melting point 162-164 C.

Refractive index: 1.4743 (21 C.)

EXAMPLE 2 (1) 2.7 g. (0.1 mole) of metallic aluminium is dissolved in 50 cc. of 2N-HC1 (0.1 mole) under heating to obtain a solution of a basic aluminium chloride whose formula is Al(OH) C1.

(2) To an aqueous solution of 47.58 g. (0.1 mole) of potassium alum (AlK(SO 'l2H O) is added a solution of sodium bicarbonate to form aluminium hydroxide. The aluminium hydroxide is dissolved in 50 cc. of 2N-HC1 with stirring and the solution is heated for 1 hour at 100 C. to give a solution of a basic aluminium chloride whose formula is Al(OH) C1.

(3) To a solution of 24.2 g. (0.1 mole) of hydrous aluminium chloride in 100 cc. of water is added gradu ally 16.8 g. (0.2 mole) of sodium bicarbonate with stirring and the solution is heated for 1 hour at 100 C. on a water-bath.

Any of the solutions of the basic aluminium chloride produced by the above three methods is diluted with water to 200 cc. and added to a solution of 28.45 g. (0.1 mole) of stearic acid and 4 g. of sodium hydroxide (0.1 mole) in 1000 cc. of water, and the mixture is heated on a Waterbath until the product precipitates. After washing with water to remove chlorine ion, the product is extracted with acetone in Soxhlets extractor to remove free stearic acid, obtaining 33 g. of aluminium monostearate Whose formula is Al(OH) (C H COO).

Aluminium monostearate produced from the basic aluminium chloride prepared by the above method (1):

Analytical value: Al, 7.24%; C H COO, 81.65% Ratio of AI:C H COO: Calcd. 1: 1, found 1:1.072 Melting point: 179190 C.

Refractive index: 1.4786 (21 C.)

Aluminium monostearate produced from the basic aluminium chloride prepared by the above method (2):

Analytical value: Al, 7.08%; C H COO, 81.19% Ratio of Al:C H CO: Calcd. 1:1, found 1:1.09. Melting point: 168170 C. Refractive index: 1:486 (21 C.)

EXAMPLE 3 A solution prepared by dissolving 5.4 g. (0.2 mole) of metallic aluminium in 50 cc. of 2N-HC1 (0.1 mole) under heating is treated with a small amount of activated charcoal and diluted with Water to 100 cc. To a solution of 28.45 g. (0.1 mole) of stearic acid and 40 g. (0.1 mole) of sodium hydroxide in 850 cc. of Water is added the above solution and the mixture is heated on a water-bath until the product precipitates. After wash ing with water to remove chlorine ion, the precipitate is dried at 100 C. and then extracted with acetone in Soxhlets extractor to remove free stearic acid, obtaining 41 g. of aluminium half-stearate whose formula is z( )5( 17 ss Analytical value: Al, 12.79%; C H COO, 67.09%

Ratio of AIIC17H35COOZ Calcd. 1:0.5, found 110.563 Refractive index: 1.5014 (21 C.)

The product does not melt but decomposes at a high temperature.

EXAMPLE 4 A solution prepared by dissolving 10.8 g. (0.4 mole) of metallic aluminium in 100 cc. of 3N-HCl (0.3 mole) under heating is treated with a small amount of activated charcoal and diluted with water to 2000 cc. The diluted solution is added to a hot solution prepared from 85.34 g. (0.3 mole) of stearic acid, 150 cc. of 2N-NaOI-I (0.3 mole) and 2550 cc. of water and the mixture is stirred until the product precipitates. After washing with water to remove chlorine ion, the precipitate is dried at 100 C. and extracted with acetone in Soxhlets extractor to remove free stearic acid, whereupon 65.6 g. of aluminium stearate with the composition of A14(0H)9(C17H35COO)3 is obtained.

Analytical value: Al, 9.19%; C17H35COO, 77.13% Ratio of Al:C H COO: Calcd. 1:075, found 1:078

EXAMPLE 5 g A solution prepared by dissolving 13.5 g. (0.5 mole) of metallic aluminium in 100 cc. of ZN-HCl (0.2 mole) under heating is treated with a small amount of activated charcoal and diluted with water to 2500 cc. The diluted solution is added to a solution of 56.90 g. (0.2 mole) of stearic acid and 100 cc. of ZN-NaOH (0.2 mole) in 1930 cc. of water under heating. After washing with water to remove chlorine ion, the product is extracted with acetone in Soxhlets extractor to remove free stearic acid, obtaining 85.6 g. of Al (OH) (C -;H COO) 10' Analytical value: Al, 13.26%; C H COO, 61.94% Ratio of AlZC1qH35COOZ Calcd. 1:0.40, found 1:0.43

EXAMPLE 6 To 300 cc. of a hot 0.1 mole/l. solution of sodium stearate (0.03 mole) is added with stirring cc. of a hot 1 mole/l. solution of a basic aluminium chloride (0.08 mole) representable by the formula of Al (OH) Cl in which the ratio of AlzCl is 8:3, whereupon a white precipitate is formed. The mixture is further stirred vigorously for a While, and the precipitate, after washing with water to remove chlorine ion completely, is dried at -105 C., whereupon 14.0 g. of aluminium stearate, in which the ratio of Al:C H COO is 8:3 (mole ratio), is obtained.

Analytical value: Al, 13.78%; C H COO, 55.27%

Ratio of Al:C -;H COO: Calcd. 120.375, found 120.38

Refractive index: 1.491 (20 C.)

The product has no melting point, but decomposes at a high temperature.

The above 1 mole/ 1. solution of the basic aluminium chloride is prepared as follows: 54 g. (2 mole) of metallic aluminium is dissolved in 365 cc. of 10% HCl (1 mole) under heating and the resulting solution of a basic aluminium chloride, in which the ratio of AlzCl is 2:1, is adjusted to 2 mole/l. solution. To the solution is added 250 cc. of N-NaOH (0.25 mole) and the mixture is vigorously stirred at a room temperature, when the resulting precipitate goes again in solution. The solution is treated with activated charcoal and diluted With water to 2000 cc.

EXAMPLE 7 To 200 cc. of a hot 0.1 mole/l. solution of sodium stearate (0.02 mole) is added with stirring vigorously 80 cc. of a hot 1 mole/l. solution of a basic aluminium chloride (0.08 mole) representable by the formula of Al (OH) C1 in which the ratio of AlzCl is 8:3 (mole ratio), and the mixture, after addition of 10 cc. of N-NaOH (0.01 mole), is stirred thoroughly on a waterbath to form a homogeneous precipitate. The precipitate is Washed with water free of chlorine ion and dried at 100-105 C., whereupon 11.5 g. of aluminium stearate, in which the ratio of AIZC17H35COO is 4:1 (mole ratio), is yielded.

Analytical value: Al, 18.03%; C H COO, 53.62%

Ratio of Al:C H COO: Calcd. 1:0.25, found 1:0.28

Refractive index: 1.4965 (20 C.)

The product does not melt but decomposes at a high temperature.

EXAMPLE 8 T o a hot solution composed of 80 cc. of 0.1 mole/l. solution of sodium stearate (0.008 mole) and 7 cc. of N-NaOH (0.007 mole) is added with stirring 40 cc. of a hot 1 mole/l. solution of a basic aluminium chloride (0.04 mole) representable by the formula of Al (OH) Cl The resulting precipitate is washed with water to remove chlorine ion completely and dried at 100-105 C., whereupon 5 g. of aluminium stearate representable by the formula of Al (OH) C H COO is obtained.

Analytical value: Al, 19.80%; C17H35COO, 44.86%

Ratio of A1ZC17H35COOI Calcd. 1:0.20, found 120.21

Refractive index:1.4965 (16.5 C.)

The product has no melting point, but decomposes at a high temperature.

EXAMPLE 9 To a hot solution composed of 50 cc. of 0.1 mole/l. solution of sodium stearate (0.005 mole) and 10 cc. of N-NaOH (0.001 mole) is added with stirring 40 cc. of a 1 mole/l. solution of a basic aluminium chloride (0.04 mole) representable by the formula of Al (OH) Cl The resulting precipitate is washed with water free of ll chlorine ion and dried at 100-105 C., whereupon 4 g. of aluminium stearate representable by the formula of A18(OH)23C17H35COO is Analytical value: Al, 24.79%; C17H35COO, 33.29% Ratio of Al:C H COO: Calcd. 1:0.125, found 1:0.127. Refractive index: 1.5015 C.) The product does not melt but decomposes at a high temperature.

EXAMPLE 10 To a hot solution composed of cc. of 0.1 mole/l. solution of sodium stearate (0.0025 mole) and 12.5 cc. of N-NaOH (0.0125 mole) is added 40 cc. of a hot 1 mole/l. solution of a basic aluminium chloride (0.04 mole) having the composition of Al (OH) Cl The mixture is vigorously stirred and the resulting precipitate is washed with water free of chlorine ion and dried at 100-105 C., whereupon 3.3 g. of aluminium stearate whose formula is Al (OH) C H COO is yielded.

Analytical value: Al, 28.75%; C H COO, 20.66% Ratio of Al:C H COO: Calcd. 1:0.0625, found 1:0.0685 Refractive index: 1.5054 (23 C.) The product has no melting point, but decomposes at a high temperature.

EXAMPLE 11 To a solution of a basic aluminium chloride (the solution contains 1% of Al) prepared by dissolving 5.4 g. (0.2 mole) of metallic aluminium in 36.5 cc. of 10% hydrochloric acid (0.1 mole) under heating is added 180 cc. of 10% solution of sodium sulfate and the mixture is heated. The resulting precipitate is washed with water, obtaining pasty basic aluminium sulfate. To the sulfate are added 448 cc. of 0.1 mole/1. solution of sodium stearate (0.0448 mole) and 44.8 cc. of N-NaOH (0.0448 mole), and the mixture is stirred. After Washing With water, the resulting precipitate is dried at 100- 105 C., whereupon 25.52 g. of aluminium stearate, in which the ratio of Al:C H COO is 4:1, is yielded.

Analytical value: Al, 17.02%; C H COO, 43.49%

Ratio of AlIC17H35COOI Calcd. 1:0.25, found 110.24

The properties of the product are in accord with those of the product of Example 7.

EXAMPLE 12 To 200 cc. of a hot 0.1 mole/l. solution of sodium stearate (0.02 mole) is added with vigorous stirring 60 cc. of a hot 1 mole/l. solution of a basic aluminium chloride (0.06 mole) representable by the formula of Al (-OH) Cl, in which the ratio of Al:Cl is 3:1. The resulting precipitate is washed with water free of chlorine ion and dried at 100-105 C., yielding 9.5 g. of aluminium stearate, in which the ratio of AkC I-I COO is 3:1.

Analytical value: Al, 15.90%; C I-1 000, 58.31%

Ratio of Al:C -;H COO: Calcd. 110.333, found 1:0;349

The product has no melting point, but decomposes at a high temperature.

The above solution of the basic aluminium chloride, in which the ratio of A1:Cl is 3:1 (mole ratio), is preq pared by dialyzing a 1 mole/l. solution of basic aluminium chloride representable by the formula of Al (OH) Cl in a cellophane, bag against flowing water for 24 hours.

EXAMPLE 13 To 100 cc. of a hot 0.1 mole/l. solution of sodium stearate (0.01 mole) is added under vigorous agitation 50 cc. of a hot 1 mole/l. solution of a basic aluminium chloride (0.05 mole) representable by the formula of Al (OH) Cl, in which the ratio of Al:Cl is 5:1 (mole ratio). The resulting precipitate is washed with water to remove chlorine ion completely and dried at 105 C., obtaining 6 g. of aluminium stearate, in which the ratio Of AIZC17H35COO is 5:1.

12 Analytical value: Al, 19.80%; C17H35COO, 44.86% Ratio of Al:C H COO: Calcd. 1:0.2, found 1:0.2155 Refractive index: 1.4965 (16.5 C.) The product has no melting point, but decomposes at a high temperature.

The above solution of the basic aluminium chloride is produced by dialyzing a 1 mole/l. solution of a basic aluminium chloride representable by the formula of Al (OH) Cl in a cellophane bag against flowing water for 9 days.

EXAMPLE 14 To a solution prepared by dissolving under heating 5.7684 g. (0.04 mole) of n-caprylic acid and 20.0 cc. of ZN-NaOH (0.04 mole) in 181 cc. of water is added 200 cc. of a hot aqueous 0.2 mole/l. solution of a basic aluminium chloride (0.04 mole) representable by the formula of Al(OH) Cl, prepared in the same manner as in Example 2. The mixture is stirred on a water bath of 100 C. to form a precipitate. After washing with water to remove chlorine ion completely, the precipitate is dried at 100 C., and extracted with acetone in Soxhlets extractor to remove free n-caprylic acid, whereupon 6.4 g. of aluminium mono-n-caprylate, in which the ratio of Al: (C H CO'O) is 1: 1, is obtained.

Analytical value: Al, 13.03%; C I-I COO, 69.13% Ratio of A1:(C7H15COO): Calcd. 1:1, found 1:0.992 Melting point: 235 C. Refractive index: 1.41 17 (22 C.)

EXAMPLE 15 To a solution prepared by dissolving under heating 9.134 g. (0.04 mole) of myristic acid and 20.00 cc. of ZN-NaOI-I (0.04 mole) in 287 cc. of water is added 200 cc.- of a hot 0.2 mole/l. solution of a basic aluminium chloride (0.04 mole) representable by the formula of Al(OI-I) Cl, prepared in the same manner as in Example 2, and the mixture is heated. The precipitate thus formed is washed with water, dried at 100 C., and extracted with acetone in Soxhlets extractor to yield 11.63 g. of aluminium monomyristate in which the ratio of Al:C H COO) is 1:1.

Analytical value: Al, 9.19%; C H COO, 80.59% Ratio of Al:(C H COO): Calcd. 1:1, found 1 21.03 Melting point: 185 C.

Refractive index: 1.4743 (23 C.)

EXAMPLE 16 To a hot solution of 7.69 g. (0.03 mole) of palmitic acid and 15 cc. of two moles/l. solution of sodium hydroxide (0.03 mole) in 215 cc. of water is added with stirring cc. of 1 mole/l. hot C.) solution of a basic aluminium chloride (0.08 mole) representable by the formula of Al (OH) Cl to form a precipitate. After washing with water, the precipitate is dried at C. to obtain 13.40 g. of aluminium palmitate representable by theforrnula of Al (OH) (C H COO) Analytical value: Al, 15.71%; C H COO, 56.34% Ratio of Al:C H COO: Calcd. 8:3, found 8.00:3.02 Refractive index: 1.4965 (20 C.) The product has no melting point, but decomposes at a high temperature.

EXAMPLE 17 To a hot solution of 4.567 g. (0.02 mole) of myristic acid and 15 cc. of 2 moles/l. solution of sodium hydroxide (0.03 mole) in 137 cc. of water is added with stirring 80 cc. of a 1 mole/l. hot solution of a basic aluminium chloride (0.08 mole) representable by the formula of Al (OI-I) Cl to form a precipitate. After washing with water, the precipitate is dried at 105 C. to obtain 10.46 g. of aluminium myrista-te representable by the formula Of 1(C 3H 7COO).

Analytical value: Al, 19.99%; C H COO, 44.11% Ratio of Al:C H COO: Calcd. 1:0.25, found 1:0.26 Refractiveindex: 1.48635 (22 C.)

The product has no melting point, but decomposes ata high temperature.

EXAMPLE "18 i To a hot solution of 2.003 g. (0.01 mole) of lauric acid Analytical value: Al, 24.97%; C I-1 000, 23.38%

Ratio of A1;c H ,coo= Calcd. 1:0.125, found 1:0.126

Refractive index: 1.4864 (20 C.)

The product does not melt but decomposes at a high temperature.

EXAMPLE 19 To a hot solution of 14.42 g. (0.1 mole) of Z-ethylhexonic acid in 50 cc. of ZN-NaOH (0.1 mole) of 60 C. is added under stirring 100 cc. of a 1 mole/l. hot solution of a basic aluminium chloride (0.1 mole) representable by the formula of Al(OH) Cl to produce a precipitate. After washing with water, the precipitate is dried at 105 C. to obtain 20.4 g. of aluminium 2-ethy1- hexonate representable by the formula of )2( 3( 2)3 2 5) Analytical value: A1, 13.24%; CqHwCOO, 67.13% Ratio of A1:C H O Calcd. 1:1, found 1:0.95 Refractive index 1.4117 (20 C.)

The product has no melting point and decomposes at a high temperature.

is xzy with an aqueous solution of 31 mole of alkali salt of a fatty acid, whereby a water-insoluble aluminium soap composed of Al+++, fatty acidand OH is obtained.

3. A process for producing Water-insoluble aluminium soap in which the ratio of aluminium to fatty acid is mm, which comprises the reaction between an aqueous solution of 1 mole of a basic aluminium chloride in which the mole ratio of aluminium to chlorine is xzy, an aqueous solution of nx/m mole of an alkali salt of a fatty acid and an aqueous solution of mole of alkali, whereby a water-insoluble aluminium soap composed of Al+++, fatty carboxylic acidand OH- is obtained.

4. The process of claim 1, wherein the basic aluminium salt is a basic aluminium sulfate.

5. The process of claim 1, wherein the fatty acid moiety of the alkali salt is a fatty acid moiety having 5 to 16 carbon atoms.

6. The process of claim 5, wherein the fatty acid is a member of the class consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palrnitic acid and stearic acid.

7. Water-insoluble aluminum soap composed of Al+++, fatty acidand OH-, in which the ratio of aluminium to fatty acid is at least 2:1.

8. Water-insoluble aluminum soap of claim 7, wherein the fatty acid is a member of the class consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid.

9. Water-insoluble aluminum soap composed of Al+++, stearic acidand OH-, in which the ratio of aluminium to stearic acid is 2:1.

EXAMPLE 10. Water-insoluble aluminum soap composed of Aluminium soaps of this invention other than those stfiaric acidand in Which he ratio o described in the preceding examples may also be produced a ni m 0 s earic acid is 5:2. through paths similar to those of the above examples. 11. Water-insoluble aluminium soap composed of The following table shows the natures of several examples Al stearic acidand OH", in which the ratio of of such aluminimum soaps. aluminium to stearic acid is 8:3.

Analytical value Ratio of AlzRCOO Melting Refractive Compounds A1m OH)3m-1J(RCOO)1\ point, index Aluminium Fatty acid 0. (23 0.)

(Al), (RG00), Calcd. Found percent percent Al(OH)(O1H COO)z 9. 02 80.05 1:2 1:1. 66 210 1. 4117 AI(OH)=(C15H31OOO)--- 8. 49 80.36 1:1 1:1. 00 203 1. 4785 Al(0H)(C15Ha1OO )1... 5.15 92.91 1=2 1:194 160 1.4785 5. 29 90. 03 1: 2 1:2. 01 166 1. 4743 10. 71 72. 91 1:1 1:0. 95 229 1. 4743 6. 02 so. 36 1:2 1:2. 00 175 1. 4743 What is claimed is: 12. Water-insoluble aluminium soap composed of 1. Aprocess for producing awater-insoluble aluminum Al+++, stearic acid" and OH-, in which the ratio of soap, which comprises subjecting to double decomposialuminium to stearic acid is 4:1. tion (1) a basic aluminum salt of the formula 13. Water-insoluble aluminium soap composed of 2+n( )3n] A1+++, stearic acid and 011-, in which the ratio of h d b aluminium to stearic acid is 5:1. w erem 1s a Posmve g an a mem er 14. Water-insoluble aluminium soap composed of selected from the group cons1st1ng of Cland i; Al+++ st earlc acid and OH 1n which the ratio of with (2) a member selected from the group cons1st1ng of aluminium to stearic acid is an alkali salt of a fatty acid and a mixture of an alkali salt 15 W te olubl a1 d f of a fatty acid with an alkali solution in an aqueous medi- A1++ 1 8 a g l compose. O um; the amount of the salt of the fatty acid being at least 31 s can: 2 m Whlch the who of equivalent to (X-) thereby obtaining a homogeneous, umlmum to steanc and Is 1 uniform product characterized by a definite refraction water'flfsolulile um s0ap composed of index Al+++, palm1t1c acldand OH-, in WhlCh the ratio of 2. Aprocess for producingawater-insoluble aluminium alumlnlum Palmltic acid soap according to claim 1 in which the mole ratio of water'lnsoluble alumlnium p composed of aluminium to fatty acid is xzy, which comprises reacting Al+++, myristic acid and in Which the ratio of an aqueous solution of 1 mole of a basic aluminium aluminium t0 myristic acid is chloride in which the mole ratio of aluminium to chlorine 18- water-insoluble aluminium soap composed of 3,056,819 15 16 A1+++, lauric acidand OH, in which the ratio of alu- 2,957,934 Bulloff Oct. 25, 1960 mim'um to lauric acid is 8:1. OTHER REFERENCES) References Cited in the file this Pawnt Rakowitz: Columbia University, 1955, Microfilm L. c.-

UNITED STATES PATENTS 5: Mic, 57-2695, Abstract in Dissentation abstracts, vol 17 2 823 144 Dalton Feb 11 95 (195.7), PP- 1578-1679 Ielied P 

1. A PROCESS FOR PRODUCING A WATER-INSOLUBLE ALUMINUM SOAP, WHICH COMPRISES SUBJECTING TO DOUBLE DECOMPOSITION (1) A BASIC ALUMIUM SALT OF THE FORMULA 